CN109742355A - A kind of preparation of silicon carbon composite materials method - Google Patents
A kind of preparation of silicon carbon composite materials method Download PDFInfo
- Publication number
- CN109742355A CN109742355A CN201811643781.0A CN201811643781A CN109742355A CN 109742355 A CN109742355 A CN 109742355A CN 201811643781 A CN201811643781 A CN 201811643781A CN 109742355 A CN109742355 A CN 109742355A
- Authority
- CN
- China
- Prior art keywords
- silicon
- carbon
- nano
- temperature
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation of silicon carbon composite materials methods, it is constituted precursor with metal organic framework ZIF-8 film package nano-silicon core-shell structure, carbon-coating package nano-silicon core-shell structure is obtained after carbon source charing is added, different carbon-coatings are obtained by the amount and charing environment that control carbon source and wrap up nano-silicon core-shell structure, while the carbon-coating that ZIF-8 film reversely replicates has continuous duct.Preparation method provided by the invention, carbon-coating be can be realized to the single continuous package of nano-silicon, nano-silicon is avoided to reunite again, body expansion, effectively control silicon powder dusting of the silicon materials in charge and discharge process is effectively relieved to inactivate, there is carbon-coating continuous duct to be conducive to the transmission of electrolyte/lithium ion simultaneously, to improve the cycle life of Si-C composite material.
Description
Technical field
The present invention relates to battery technology fields, and in particular to a kind of technology of preparing of lithium ion battery composite material.
Background technique
Current commercialized lithium ion battery negative material is mainly graphite cathode material, and theoretical specific capacity only has
372mAh/g, and silicon has high theoretical specific capacity -4200mAh/g, by people's extensive concern.But its relatively low conductivity, and
It is silicon materials dusting as 300% expansion and contraction occurs for the insertion of lithium ion and abjection silicon volume in charge and discharge process,
It eventually leads to it and is detached from inactivation with collector, substantially reduce cycle performance of battery.
In view of the above problems, currently used solution is silicon materials to be carried out to nanosizing, and preparation silicon substrate is compound
Material forms buffer layer by package silicon materials, reduces silicon materials bulk effect, improve its cycle life.
Metal organic framework (metal organic frameworks, MOF) is by metal ion or metal cluster and organic
Ligand acts on a kind of porous crystalline material made of self assembly by covalent or ionic-covalent.MOFs material has high-ratio surface
Outstanding advantages of product, porosity, adjustable pore structure, but the thermal stability of MOFs material is poor, according to its labile spy that is heated
Its high-temperature calcination is carbonized to prepare and stablizes porous carbon materials by point.Such as " hydrophobicity is double for patent (application number 201810773309.2)
" a kind of derivative porous carbon/graphene of MOF is multiple for the preparation of MOF base porous carbon materials ", patent (application number 201810036535.2)
Composite electrode material " and patent (application number 201710504003.2) " MOF structural porous carbon material, flexible super capacitor, its system
Preparation Method and purposes " etc. is to prepare porous carbon materials by MOFs material.
Silicon materials particle size used by commercialized silicon composite is other in the micron-scale at this stage, main cause:
First is that silicon materials nanosizing is difficult；Second is that agglomeration is serious again for nano silicon material.
Summary of the invention
For the problems of existing silicon-carbon complex technique, a kind of new silicon-carbon complex technique is needed.
For this purpose, carbon-coating can be formed to nano-silicon the purpose of the present invention is to provide a kind of preparation of silicon carbon composite materials method
Single continuous package, avoid nano-silicon from reuniting again, at the same carbon-coating have continuous duct Si-C composite material.
In order to achieve the above object, preparation of silicon carbon composite materials method provided by the invention, with metal organic framework ZIF-8
It is precursor that film, which wraps up nano-silicon core-shell structure, and acquisition carbon-coating wraps up nano-silicon core-shell structure after carbon source carbonization is added, and passes through control
The amount and charing environment of carbon source processed obtain different carbon-coating package nano-silicon core-shell structures, while the carbon-coating that ZIF-8 film reversely replicates
With continuous duct.
Further, the preparation method includes:
(1) nano-silicon is surface modified；
(2) nano-silicon after modifying is scattered in ZIF-8 Synthesis liquid, in the ZIF-8 film layer of its surface growth continuous uniform, obtains
ZIF-8 film wraps up nano-silicon core-shell structure；
(3) ZIF-8 film is wrapped up into nano-silicon core-shell structure and carbon source mixes, Si-C composite material is obtained after charing, simultaneously
The further chemical vapor deposition nano-sized carbon of carbon-source gas is passed through in carbonization process.
Further, the nano-silicon is one or more of silicon, Si oxide and metal silicide.
Further, in the step (1) using PDDA or/and PSS come to nano-silicon surface modification.
Further, the carbon source be one of glucose, sucrose, phenolic resin, furfural resin and hard pitch or
It is a variety of.
Further, the carbon-source gas is one of methane acetylene, propane, propylene and acetonitrile or a variety of.
Further, the carbonization process, point four temperature sections are realized, specific as follows:
It first is warming up to Y1 DEG C of carbonization temperature from room temperature with the heating rate of x DEG C/min, then keeps the temperature c1 hours；
It is warming up to Y2 DEG C of carbonization temperature with the heating rate of x DEG C/min again, then keeps the temperature c2 hours；
After be passed through nitrogen/argon gas inert gas, then be warming up to Y3 DEG C of carbonization temperature with the heating rate of x DEG C/min, be passed through
Carbon-source gas keeps the temperature c3 hours；
It still finally is warming up to Y4 DEG C of carbonization temperature under nitrogen/argon gas inert gas, then with the heating rate of x DEG C/min,
Then c4 hours are kept the temperature.
Wherein, 3≤x≤10,150≤Y1≤80≤Y2≤300≤Y3≤700≤Y4≤1100,1≤c1, c2, c3, c4
≤16。
Scheme provided by the invention wraps up nano-silicon core-shell structure precursor by synthesis ZIF-8, obtains after carbon source carbonization
Carbon-coating wraps up nano-silicon core-shell structure, realizes that nano silicone material is isolated, avoids silicon materials from reuniting again, silicon materials are effectively relieved and exist
In charge and discharge process body expansion, effectively control silicon powder dusting inactivation, while carbon-coating have continuous duct be conducive to electrolyte/
The transmission of lithium ion, to improve the cycle life of Si-C composite material.
Detailed description of the invention
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.
Fig. 1 is the charging and discharging curve figure of 1 gained Si-C composite material of embodiment；
Fig. 2 is 1 gained Si-C composite material of embodiment under 8.8mA/cm current density, 100 appearances recycled of discharging
Measure change curve.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Conjunction is specifically illustrating, and the present invention is further explained.
Carbon source charcoal is added using metal organic framework ZIF-8 film package nano-silicon core-shell structure as precursor in this example approach
Carbon-coating is obtained after change and wraps up nano-silicon core-shell structure, and different carbon-coatings are obtained by the amount and charing environment that control carbon source and wrap up nanometer
Silicon core-shell structure, while the carbon-coating that ZIF-8 film reversely replicates has continuous duct.Carbon-coating wraps up nano-silicon core-shell structure, can
Realize that carbon-coating to the single continuous package of nano-silicon, avoids nano-silicon from reuniting again, silicon materials are effectively relieved in charge and discharge process
Body expansion, effectively control silicon powder dusting inactivation, while carbon-coating have continuous duct be conducive to electrolyte/lithium ion biography
It is defeated, to improve the cycle life of Si-C composite material.
Based on the following this principle, the process of Si-C composite material is prepared come illustratively this example.
This example, firstly, being surface modified to nano-silicon.
In this example using PDDA and PSS (phthalic acid diethylene glycol diacrylate and kayexalate) come
Nano-silicon is surface modified, nano-silicon dispersion can be conducive in this way, inhibit the reuniting effect between nano silica fume.
In addition, the nano-silicon employed in this example is one or more of silicon, Si oxide and metal silicide, it is somebody's turn to do
The median particle diameter of nano-silicon is preferably 1-500nm.Because nano silicone material is in charge and discharge process, relative to the body of itself
Bulking effect is constant, but for tens to several hundred micron levels electrode, body bulking effect is smaller, is conducive to prolong
Long battery cycle life.
Then, ZIF-8 Synthesis liquid is dispersed by the nano-silicon after modification, respectively after low temperature, stirring at normal temperature, in nano-silicon table
It looks unfamiliar the ZIF-8 film layer of long continuous uniform, obtains ZIF-8 film package nano-silicon core-shell structure.
Finally, obtained ZIF-8 film is wrapped up nano-silicon core-shell structure and carbon source mixing, it is multiple that silicon-carbon is obtained after being carbonized
Condensation material, while the further chemical vapor deposition nano-sized carbon of carbon-source gas is passed through in carbonization process.
It is carbonized after mixing ZIF-8 film package nano-silicon core-shell structure with carbon source in this example, point four temperature sections are real
It is existing, specific as follows:
It first is warming up to Y1 DEG C of carbonization temperature from room temperature with the heating rate of x DEG C/min, then keeps the temperature c1 hours；
It is warming up to Y2 DEG C of carbonization temperature with the heating rate of x DEG C/min again, then keeps the temperature c2 hours；
After be passed through nitrogen/argon gas inert gas, then be warming up to Y3 DEG C of carbonization temperature with the heating rate of x DEG C/min, be passed through
Carbon-source gas keeps the temperature c3 hours；
It still finally is warming up to Y4 DEG C of carbonization temperature under nitrogen/argon gas inert gas, then with the heating rate of x DEG C/min,
Then c4 hours are kept the temperature.
Wherein, 3≤x≤10,150≤Y1≤80≤Y2≤300≤Y3≤700≤Y4≤1100,1≤c1, c2, c3, c4
≤16。
Divide four temperature sections to realize charing, main effect is as follows: one Y1 of temperature section realizes the prepolymerization of carbon source here；Temperature section
Two Y2 realize preliminary charing；Three Y3 of temperature section realizes the charing of carbon source, while carrying out the chemical vapor deposition of certain time c3；
Four Y4 of temperature section realizes the degree of graphitization for improving carbon-coating under high temperature.
The carbon source used in this example is preferably one in glucose, sucrose, phenolic resin, furfural resin and hard pitch
Kind is a variety of.
The carbon-source gas of carry out chemical vapor deposition in this example is preferably in methane acetylene, propane, propylene and acetonitrile
It is one or more.
The Si-C composite material according to prepared by above scheme, uses ZIF-8 continuously to wrap up nano-silicon, using it as template
The carbon-coating of charing also continuously wraps up nano-silicon, realizes that carbon-coating to the single continuous package of nano-silicon, is effectively relieved silicon materials and is filling
Body expansion, effectively control silicon powder dusting in discharge process inactivate；The carbon-coating that ZIF-8 is reversely replicated simultaneously has continuous duct,
Be conducive to the transmission of electrolyte/lithium ion.
For above scheme, carry out illustratively this programme below by way of specific application example.
Embodiment 1
This example prepares Si-C composite material as follows based on above scheme:
A) 100nm is aoxidized into sub- Si powder ultrasonic disperse in aqueous solution, 20min is mixed with PDDA aqueous solution, often
Temperature stands 30min, and with deionized water, eccentric cleaning is multiple under 8000r/min revolving speed；It is mixed again with PSS aqueous solution
After 20min, room temperature stands 30min, multiple with deionized water, methanol eccentric cleaning under 8000r/min revolving speed respectively.
B) nano-silicon for having modified PDDA/PSS for obtaining step a) is scattered in ZIF-8 stoste, ice bath stirring 2h, often
Temperature stirring 1h；Wherein, the group of stoste becomes 2-methylimidazole, zinc nitrate and methanol, and the mol ratio of stoste is about are as follows: 2- methyl miaow
Azoles: zinc nitrate: methanol=10:1:810；It is achieved in the ZIF-8 film layer in silicon powder surface growth continuous uniform, obtains ZIF-8
Film wraps up nano-silicon core-shell structure, and obtained ZIF-8 film package is dried in vacuum overnight for 60 DEG C of nano-silicon core-shell structure.
C) the ZIF-8 film package nano-silicon core-shell structure that step b) is obtained is added to containing 12mL furfuryl alcohol, 0.24g oxalic acid
And 100mL1, the mixed solution mL of 3,5- trimethylbenzenes, acquisition just wetting is sufficiently stirred at room temperature, then by mixture 60
Prepolymerization is realized with 16h is kept the temperature in 80 DEG C of air respectively.
Under gained powder nitrogen atmosphere, then 150 DEG C of heat preservation 3h are raised to 300 DEG C with the heating rate of 5 DEG C/min, then with 5
DEG C/heating rate of min is raised to 700 DEG C.When temperature is raised to 700 DEG C, carries out chemical vapor deposition: nitrogen being first passed through acetonitrile
In solution, then the nitrogen gas for being contaminated with acetonitrile component is passed through in tube furnace, in 700 DEG C of heat preservation 4h, then is changed to nitrogen,
It is warming up to 900 DEG C under nitrogen atmosphere and keeps the temperature 1h.
It is cooling under last nitrogen protection to obtain Si-C composite material 1.
Embodiment 2
This example carries out on the basis of example 1, and basic implementation process is identical as in embodiment 1, is not gone to live in the household of one's in-laws on getting married herein
It states, the difference is that, this example includes the following steps:
C) the 40g ZIF-8 film package nano-silicon core-shell structure that step b) is obtained is added to containing 12mL furfuryl alcohol, 0.24g
Acquisition just wetting is sufficiently stirred, then by mixture in oxalic acid and 100mL1, the mixed solution mL of 3,5- trimethylbenzenes at room temperature
It keeps the temperature 16h respectively in 60 and 80 DEG C of air and realizes prepolymerization.
Under gained powder nitrogen atmosphere, then 150 DEG C of heat preservation 3h are raised to 300 DEG C with the heating rate of 5 DEG C/min, then with 5
DEG C/heating rate of min is raised to 700 DEG C.When temperature is raised to 700 DEG C, carries out chemical vapor deposition: nitrogen being first passed through acetonitrile
In solution, then the nitrogen gas for being contaminated with acetonitrile component is passed through in tube furnace, in 700 DEG C of heat preservation 2h, then is changed to nitrogen,
It is warming up to 900 DEG C under nitrogen atmosphere and keeps the temperature 1h.
It is cooling under last nitrogen protection to obtain Si-C composite material 2.
Embodiment 3
This example carries out on the basis of example 1, and basic implementation process is identical as in embodiment 1, is not gone to live in the household of one's in-laws on getting married herein
It states, the difference is that, this example includes the following steps:
C) 40g ZIF-8 film b) obtained package nano-silicon core-shell structure is added to containing 12mL furfuryl alcohol, 0.24g oxalic acid
And 100mL1, the mixed solution mL of 3,5- trimethylbenzenes, acquisition just wetting is sufficiently stirred at room temperature, then by mixture 60
Prepolymerization is realized with 16h is kept the temperature in 80 DEG C of air respectively.Under gained powder nitrogen atmosphere, 150 DEG C of heat preservation 3h, then with 5 DEG C/
The heating rate of min is raised to 300 DEG C, then is raised to 700 DEG C with the heating rate of 5 DEG C/min.When temperature is raised to 700 DEG C, carry out
Nitrogen: being first passed through in acetonitrile solution by chemical vapor deposition, then the nitrogen gas for being contaminated with acetonitrile component is passed through in tube furnace,
In 700 DEG C of heat preservation 6h, then it is changed to nitrogen, be warming up to 900 DEG C in a nitrogen atmosphere and keeps the temperature 1h.
It is cooling under last nitrogen protection to obtain Si-C composite material 3.
Embodiment 4,
This example carries out on the basis of example 1, the difference is that, this example includes the following steps:
A) by 100nm nano-silicon powder ultrasonic disperse in aqueous solution, 20min, room temperature is mixed with PDDA aqueous solution
30min is stood, eccentric cleaning is multiple under 8000r/min revolving speed with deionized water；20min is mixed with PSS aqueous solution again
Afterwards, room temperature stands 30min, multiple with deionized water, methanol eccentric cleaning under 8000r/min revolving speed respectively.
Other implementation steps are identical as in embodiment 1 in this example, will not be repeated here herein, multiple thus to obtain silicon-carbon
Condensation material 4.
For the obtained Si-C composite material 1-4 of embodiment 1-4, following experimental test is carried out.
Battery assembly: the Si-C composite material 1-4 that embodiment 1-4 is prepared is fine with conductive black, carboxymethyl respectively
It ties up plain sodium, butadiene-styrene rubber and slurry is made using weight ratio 90:5:2:3 mixing, by solvent dispersion of deionized water, coated in 9 μm
On copper foil, negative electrode is made in drying.
It is tested: making button half-cell using metal lithium sheet as positive electrode, tested, with current density 8.8mA/
Cm2 carries out charge and discharge cycles, and test result is listed in Table 1 below.
The performance test results of 1. Si-C composite material of table
Meanwhile referring to Fig. 1 which shows the charging and discharging curve figure of 1 gained Si-C composite material 1 of embodiment；
Referring to fig. 2 which shows 1 gained Si-C composite material of embodiment under 8.8mA/cm current density, electric discharge 100
The volume change curve graph of a circulation.
It can be seen from figure 1 that the discharge capacity for the first time of Si-C composite material 1 is 1659mAh/g, initial charge capacity is
1079mAh/g, head effect are 65.0%.The decline of 1 initial capacity of Si-C composite material is obvious as can be seen from Figure 2, base after 20 times
Originally reach balance, it can be achieved that normal cycle life.
As can be seen from Table 1, sub- silicon composite is aoxidized for 100nm, with the extension of CVD time, from 2h to 4h to
6h, head effect are constantly reduced, to 64.8% from 65.6% to 65.0%；When the CVD time is 2h, 100 times cycle life is
85.4%, CVD time 4 and when 6h, 100 times cycle life is close.And for 100nm silicon powder composite material, head effect is higher than oxygen
Change sub- silicon materials, but 100 cycle lives are significantly lower than the sub- silicon materials of oxidation.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (8)
1. a kind of preparation of silicon carbon composite materials method, which is characterized in that wrap up nano-silicon nucleocapsid with metal organic framework ZIF-8 film
Structure is precursor, obtains carbon-coating package nano-silicon core-shell structure after carbon source charing is added, passes through the amount and charing for controlling carbon source
Environment obtains different carbon-coating package nano-silicon core-shell structures, while the carbon-coating that ZIF-8 film reversely replicates has continuous duct.
2. preparation of silicon carbon composite materials method according to claim 1, which is characterized in that the preparation method includes:
(1) nano-silicon is surface modified；
(2) nano-silicon after modifying is scattered in ZIF-8 Synthesis liquid, in the ZIF-8 film layer of its surface growth continuous uniform, obtains
ZIF-8 film wraps up nano-silicon core-shell structure；
(3) ZIF-8 film is wrapped up into nano-silicon core-shell structure and carbon source mixes, Si-C composite material is obtained after charing, while in charcoal
The further chemical vapor deposition nano-sized carbon of carbon-source gas is passed through during changing.
3. preparation of silicon carbon composite materials method according to claim 2, which is characterized in that the nano-silicon is silicon, silicon oxygen
One or more of compound and metal silicide.
4. preparation of silicon carbon composite materials method according to claim 2, which is characterized in that used in the step (1)
PDDA or/and PSS is surface modified nano-silicon.
5. preparation of silicon carbon composite materials method according to claim 2, which is characterized in that the carbon source is glucose, sugarcane
One of sugar, phenolic resin, furfural resin and hard pitch are a variety of.
6. preparation of silicon carbon composite materials method according to claim 2, which is characterized in that the carbon-source gas is methane second
One of alkynes, propane, propylene and acetonitrile are a variety of.
7. preparation of silicon carbon composite materials method according to claim 2, which is characterized in that the carbonization process, point four temperature
Duan Shixian is spent, specific as follows:
It first is warming up to Y1 DEG C of carbonization temperature from room temperature with the heating rate of x DEG C/min, then keeps the temperature c1 hours；
It is warming up to Y2 DEG C of carbonization temperature with the heating rate of x DEG C/min again, then keeps the temperature c2 hours；
After be passed through inert gas, then be warming up to Y3 DEG C of carbonization temperature with the heating rate of x DEG C/min, be passed through carbon-source gas, keep the temperature
C3 hours；
Finally still under inert gas, then with the heating rate of x DEG C/min it is warming up to Y4 DEG C of carbonization temperature, then keeps the temperature c4 hours.
Wherein, 3≤x≤10,150≤Y1≤80≤Y2≤300≤Y3≤700≤Y4≤1100,1≤c1, c2, c3, c4≤16.
8. preparation of silicon carbon composite materials method according to claim 7, which is characterized in that the temperature of the chemical vapor deposition
Degree and time are respectively Y3 DEG C of temperature and charing soaking time c3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811643781.0A CN109742355B (en) | 2018-12-29 | 2018-12-29 | Preparation method of silicon-carbon composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811643781.0A CN109742355B (en) | 2018-12-29 | 2018-12-29 | Preparation method of silicon-carbon composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109742355A true CN109742355A (en) | 2019-05-10 |
| CN109742355B CN109742355B (en) | 2022-02-11 |
Family
ID=66362645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811643781.0A Active CN109742355B (en) | 2018-12-29 | 2018-12-29 | Preparation method of silicon-carbon composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109742355B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110867572A (en) * | 2019-11-25 | 2020-03-06 | 天津工业大学 | Preparation method of double-layer carbon-coated silicon composite material |
| CN111575686A (en) * | 2020-06-11 | 2020-08-25 | 青田永拓金属表面技术处理有限公司 | Wear-resistant corrosion-resistant high-phosphorus plating solution for surface of stainless steel ball valve and wear-resistant corrosion-resistant preparation method |
| CN112467136A (en) * | 2020-09-09 | 2021-03-09 | 珠海中科兆盈丰新材料科技有限公司 | Preparation method of silicon-carbon composite negative electrode material |
| CN113571683A (en) * | 2021-08-05 | 2021-10-29 | 山东大学 | Carbon-silicon negative electrode material, preparation method thereof and application thereof in lithium ion battery |
| CN113629251A (en) * | 2021-07-09 | 2021-11-09 | 江苏科技大学 | Self-supporting nitrogen-doped porous carbon-coated silicon nanofiber material for lithium ion battery cathode and preparation method and application thereof |
| CN114335533A (en) * | 2021-12-16 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Negative electrode material and battery comprising same |
| CN114497518A (en) * | 2022-01-20 | 2022-05-13 | 上海兰钧新能源科技有限公司 | Negative active material, preparation method thereof and negative pole piece |
| CN115020670A (en) * | 2022-06-30 | 2022-09-06 | 合肥国轩高科动力能源有限公司 | MOFs modified silicon-based negative electrode material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593426A (en) * | 2011-05-07 | 2012-07-18 | 天津锦美碳材科技发展有限公司 | Method for preparing silicon oxide (SiOx) / carbon (C) composite materials and prepared silicon carbon cathode materials for lithium ion battery |
| CN105280890A (en) * | 2014-08-27 | 2016-01-27 | 深圳市国创新能源研究院 | Core-shell structured silicon carbon composite negative electrode material and preparation method thereof |
| CN105655564A (en) * | 2016-03-30 | 2016-06-08 | 深圳市国创新能源研究院 | SiO<x>/C composite cathode material, method for preparing same and application of SiO<x>/C composite cathode material |
| CN106257714A (en) * | 2015-12-21 | 2016-12-28 | 上海卡耐新能源有限公司 | A kind of new system lithium ion battery and preparation method thereof |
| CN107359326A (en) * | 2017-06-26 | 2017-11-17 | 江苏师范大学 | A kind of Si@C lithium ion battery negative materials with core shell structure and preparation method thereof |
| US20180151865A1 (en) * | 2016-11-30 | 2018-05-31 | Samsung Sdi Co., Ltd. | Composite cathode active material, and cathode and lithium battery comprising composite cathode active material |
| CN108682813A (en) * | 2018-05-10 | 2018-10-19 | 厦门大学 | A kind of preparation method and application of Si-C composite material |
-
2018
- 2018-12-29 CN CN201811643781.0A patent/CN109742355B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593426A (en) * | 2011-05-07 | 2012-07-18 | 天津锦美碳材科技发展有限公司 | Method for preparing silicon oxide (SiOx) / carbon (C) composite materials and prepared silicon carbon cathode materials for lithium ion battery |
| CN105280890A (en) * | 2014-08-27 | 2016-01-27 | 深圳市国创新能源研究院 | Core-shell structured silicon carbon composite negative electrode material and preparation method thereof |
| CN106257714A (en) * | 2015-12-21 | 2016-12-28 | 上海卡耐新能源有限公司 | A kind of new system lithium ion battery and preparation method thereof |
| CN105655564A (en) * | 2016-03-30 | 2016-06-08 | 深圳市国创新能源研究院 | SiO<x>/C composite cathode material, method for preparing same and application of SiO<x>/C composite cathode material |
| US20180151865A1 (en) * | 2016-11-30 | 2018-05-31 | Samsung Sdi Co., Ltd. | Composite cathode active material, and cathode and lithium battery comprising composite cathode active material |
| CN107359326A (en) * | 2017-06-26 | 2017-11-17 | 江苏师范大学 | A kind of Si@C lithium ion battery negative materials with core shell structure and preparation method thereof |
| CN108682813A (en) * | 2018-05-10 | 2018-10-19 | 厦门大学 | A kind of preparation method and application of Si-C composite material |
Non-Patent Citations (1)
| Title |
|---|
| HAO WANG ET AL: "ZIF-8-Templated Hollow Cubelike Si/SiO2@C Nanocomposites for Superior Lithium Storage Performance", 《APPLIED ENERGY MATERIALS》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110867572A (en) * | 2019-11-25 | 2020-03-06 | 天津工业大学 | Preparation method of double-layer carbon-coated silicon composite material |
| CN111575686A (en) * | 2020-06-11 | 2020-08-25 | 青田永拓金属表面技术处理有限公司 | Wear-resistant corrosion-resistant high-phosphorus plating solution for surface of stainless steel ball valve and wear-resistant corrosion-resistant preparation method |
| CN112467136A (en) * | 2020-09-09 | 2021-03-09 | 珠海中科兆盈丰新材料科技有限公司 | Preparation method of silicon-carbon composite negative electrode material |
| CN113629251A (en) * | 2021-07-09 | 2021-11-09 | 江苏科技大学 | Self-supporting nitrogen-doped porous carbon-coated silicon nanofiber material for lithium ion battery cathode and preparation method and application thereof |
| CN113571683A (en) * | 2021-08-05 | 2021-10-29 | 山东大学 | Carbon-silicon negative electrode material, preparation method thereof and application thereof in lithium ion battery |
| CN113571683B (en) * | 2021-08-05 | 2023-01-13 | 山东大学 | Carbon-silicon negative electrode material, preparation method thereof and application thereof in lithium ion battery |
| CN114335533A (en) * | 2021-12-16 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Negative electrode material and battery comprising same |
| CN114497518A (en) * | 2022-01-20 | 2022-05-13 | 上海兰钧新能源科技有限公司 | Negative active material, preparation method thereof and negative pole piece |
| CN115020670A (en) * | 2022-06-30 | 2022-09-06 | 合肥国轩高科动力能源有限公司 | MOFs modified silicon-based negative electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109742355B (en) | 2022-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109742355A (en) | A kind of preparation of silicon carbon composite materials method | |
| CN107359326B (en) | Si @ C lithium ion battery cathode material with core-shell structure and preparation method thereof | |
| CN109003825B (en) | Preparation method of nitrogen-doped carbon/nickel oxide nano composite material | |
| Du et al. | Strategies to succeed in improving the lithium-ion storage properties of silicon nanomaterials | |
| CN103384007B (en) | Carbon nano tube/graphene composite negative pole and preparation method thereof, lithium battery | |
| CN110649236A (en) | Porous silicon-carbon composite material and preparation method thereof | |
| CN113224279B (en) | Silica-based composite negative electrode material capable of improving first coulombic efficiency and preparation method thereof | |
| CN104103821B (en) | The preparation method of silicon-carbon cathode material | |
| CN105470511B (en) | The preparation method of tin-cobalt alloy situ catalytic three-dimensional grapheme/tin/carbon nanometer pipe composite material | |
| CN108962632B (en) | Preparation method of graphene/nitrogen-doped carbon/nickel oxide composite material | |
| CN105705460A (en) | Method for preparing hollow silicon spheres as well as hollow silicon spheres prepared therefrom | |
| CN111816855B (en) | Preparation method of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material | |
| CN110611092B (en) | Preparation method of nano silicon dioxide/porous carbon lithium ion battery cathode material | |
| CN106024424A (en) | Nickel hydroxide/graphene roll-carbon nano-tube composite carbon aerogel, preparation thereof and application thereof | |
| CN112952059A (en) | Silicon-based negative electrode material and preparation method and application thereof | |
| CN101521273B (en) | In-situ synthesis method for preparing tin-carbon/core-shell nano-particle fully filled carbon nano-tube composite anode material | |
| WO2023093448A1 (en) | Silicon-carbon negative electrode material of lithium-ion battery, preparation method therefor and application thereof | |
| CN110649254B (en) | Lithium battery silicon-carbon negative electrode composite material and preparation method thereof | |
| CN114156456B (en) | High-capacity rapid charge-discharge graphene @ hard carbon composite material, preparation method thereof and application of composite material in sodium ion battery | |
| CN113871598B (en) | MOF composite material and preparation method and application thereof | |
| Zhang et al. | Shaddock wadding created activated carbon as high sulfur content encapsulator for lithium-sulfur batteries | |
| Zhang et al. | Preparation and electrochemical properties of MOF-derived nitrogen self-doped porous carbon | |
| CN111584838B (en) | Porous silicon/silicon-carbon composite material and preparation method and application thereof | |
| WO2023217240A1 (en) | Cavity-customized carbon-silicon composite material, and preparation method therefor and use thereof | |
| CN112456457A (en) | Asphalt-based multi-layer graphite flake/red phosphorus composite nano material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |